CN103965141A - Pyrrolidine ionic liquid, and preparation method, electrolyte and capacitor thereof - Google Patents
Pyrrolidine ionic liquid, and preparation method, electrolyte and capacitor thereof Download PDFInfo
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- CN103965141A CN103965141A CN201310042656.5A CN201310042656A CN103965141A CN 103965141 A CN103965141 A CN 103965141A CN 201310042656 A CN201310042656 A CN 201310042656A CN 103965141 A CN103965141 A CN 103965141A
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- ionic liquid
- tetramethyleneimine
- preparation
- pyrrolidine
- negatively charged
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- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 title claims abstract description 125
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 65
- 239000003792 electrolyte Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000003990 capacitor Substances 0.000 title abstract 3
- -1 alkyl pyrrolidine halide Chemical class 0.000 claims abstract description 42
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims abstract description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 49
- 150000002500 ions Chemical class 0.000 claims description 27
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 238000000605 extraction Methods 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 14
- 238000001291 vacuum drying Methods 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 12
- 150000001350 alkyl halides Chemical class 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 239000008151 electrolyte solution Substances 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 101710134784 Agnoprotein Proteins 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 238000001556 precipitation Methods 0.000 claims description 7
- 229920006395 saturated elastomer Polymers 0.000 claims description 7
- 238000004448 titration Methods 0.000 claims description 7
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 239000002041 carbon nanotube Substances 0.000 claims description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical group 0.000 claims description 5
- 150000003949 imides Chemical class 0.000 claims description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 5
- 238000005342 ion exchange Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical group [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 3
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical group [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 3
- 230000004888 barrier function Effects 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 229910052740 iodine Chemical group 0.000 claims description 3
- 229910001415 sodium ion Inorganic materials 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 239000006258 conductive agent Substances 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 229910001414 potassium ion Inorganic materials 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 abstract 2
- 150000001450 anions Chemical class 0.000 abstract 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 abstract 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical compound [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- 238000011160 research Methods 0.000 description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical class [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 229910020808 NaBF Inorganic materials 0.000 description 1
- RMLHVYNAGVXKKC-UHFFFAOYSA-N [SH2]=N.C(F)(F)F Chemical compound [SH2]=N.C(F)(F)F RMLHVYNAGVXKKC-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 1
- KMGBZBJJOKUPIA-UHFFFAOYSA-N butyl iodide Chemical compound CCCCI KMGBZBJJOKUPIA-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- OPLFGPGOQRYQNK-UHFFFAOYSA-N ethane 1-methoxy-4-[2,2,2-trichloro-1-(4-methoxyphenyl)ethyl]benzene Chemical compound CC.C1=CC(OC)=CC=C1C(C(Cl)(Cl)Cl)C1=CC=C(OC)C=C1 OPLFGPGOQRYQNK-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910001412 inorganic anion Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
- C07D295/08—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms
- C07D295/084—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
- C07D295/088—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Pyrrole Compounds (AREA)
- Secondary Cells (AREA)
Abstract
The invention relates to a pyrrolidine ionic liquid and a preparation method thereof. The preparation method comprises: 1, preparing alkyl pyrrolidine halide; and 2, preparing the pyrrolidine ionic liquid. The pyrrolidine ionic liquid has a general formula (IV); in the formula (IV), Y<-> is tetrafluoroborate anion, hexafluorophosphate anion, trifluoromethylsulfonylimide anion or trifluoromethylsulfonic acid anion; and R is methoxy alkyl group represented by formula (III) of CH3O(CH2)n, and n is 2, 3 or 4. The invention also relates to an ionic liquid electrolyte prepared by using the pyrrolidine ionic liquid and, and an application of the ionic liquid electrolyte in a capacitor. The pyrrolidine ionic liquid electrolyte has substantially better stability and safety than present commercial electrolytes due to the addition of a large amount of the ionic liquid, and super capacitors using the pyrrolidine ionic liquid electrolyte have excellent electrochemical performances.
Description
Technical field
The present invention relates to the ionogen field of electrical condenser, particularly a kind of tetramethyleneimine ionic liquid and preparation method thereof.The invention still further relates to electrolytic solution prepared by this tetramethyleneimine ionic liquid and the application in electrical condenser thereof.
Background technology
Ionic liquid (Ionic liquids) (is generally below 100 ℃) and is in a liquid state in room temperature range, and consists of organic cation and inorganic anion (or organic anion).Ionic liquid has adjustability, need to change its zwitterion structure, and then reach planner's object, thereby ionic liquid is called as planner's solvent according to difference.
As far back as 1914, just found first ionic liquid-nitro ethamine, but the progress in this field is slow thereafter.Until 1992, Wikes leader's research group has synthesized low melting point, resistant to hydrolysis, 1-ethyl-3-methylimidazole tetrafluoroborate ion liquid ([EMIM] BF that stability is strong
4) after, the research of ionic liquid is just developed rapidly, has developed subsequently a series of ion liquid system.Initial ionic liquid is mainly used in electrochemical research, and ionic liquid comes into one's own for organic and Polymer Synthesizing as green solvent in recent years.Ionic liquid has been obtained many gratifying results as the research in the fields such as the novel solvent of a class, medium, extracting and separating, material preparation, natural polymer, electrochemistry, has been subject to paying close attention to widely.
Compare with ionogen with traditional organic solvent, ionic liquid has advantages of a series of outstanding, as large in equilibrium temperature scope, can be recycled, free from environmental pollution etc.But its stability, security and the chemical property while being applied to electrical condenser all have much room for improvement.
Summary of the invention
The first object of the present invention is to provide a kind of all preparation method methods of good tetramethyleneimine ionic liquid of security, chemical property.
The second object of the present invention is to provide above-mentioned tetramethyleneimine ionic liquid.
The 3rd object of the present invention is to provide a kind of il electrolyte of being prepared by described tetramethyleneimine ionic liquid.
The 4th object of the present invention is to provide a kind of electrical condenser of being prepared by described il electrolyte.
In order to realize the first object of the present invention, the technical solution adopted in the present invention is: a kind of preparation method of tetramethyleneimine ionic liquid, comprises the steps:
(a) prepare alkyl pyrrolidine halogenide: crassitude and the haloalkane RX reaction with following logical formula I are made to the alkyl pyrrolidine halogenide with following logical formula II,
Wherein, X is halogen; R is the methoxyl group alkyl with following logical formula III:
CH
3o (CH
2)
n(III), wherein, n is 2,3 or 4;
(b) prepare tetramethyleneimine ionic liquid: the alkyl pyrrolidine halogenide that described step (a) is made and inorganic salt MY and deionized water carry out ion exchange reaction, obtain having the described tetramethyleneimine ionic liquid of following logical formula IV,
Wherein, Y
-for Tetrafluoroboric acid negatively charged ion, phosphofluoric acid negatively charged ion, trifluoromethanesulp-onyl-onyl imide negatively charged ion or trifluoromethane sulfonic acid negatively charged ion;
R is the methoxyl group alkyl with following logical formula III: CH
3o (CH
2)
n(III), wherein, n is 2,3 or 4;
M is sodium ion, potassium ion or ammonium ion.
Described step (a) is specially: under protection of inert gas; after 1:1.05 ~ 1.2 mixed methyl tetramethyleneimine and haloalkane RX, be warmed up in molar ratio 60 ~ 80 ℃ and stir 20 ~ 60h; standing cooling, with after ethyl acetate washing, through vacuum-drying, obtain alkyl pyrrolidine halogenide.
The preferred molar ratio of described crassitude and described haloalkane is 1:1.1.
Described step (b) is specially: getting described alkyl pyrrolidine halogenide, inorganic salt and deionized water is to stir after 1mol:1 ~ 1.1mol:200 ~ 300ml mixes by mole volume ratio, to mixed solution described in the described dichloromethane extraction of 250ml for the mixed solution obtaining, the extraction liquid obtaining is stripped with 60ml deionized water, until with saturated AgNO
3till aqueous solution titration water produces without precipitation, the methylene dichloride of collecting is concentrated with Rotary Evaporators, after vacuum-drying, obtain tetramethyleneimine ionic liquid;
The preferred molar ratio of described alkyl pyrrolidine halogenide and described inorganic salt is 1:1.05.
Described halogen X is chlorine, bromine or iodine atom.
In order to realize the second object of the present invention, the technical solution adopted in the present invention is: a kind of tetramethyleneimine ionic liquid with following logical formula IV being made by aforesaid method,
Wherein, Y
-for Tetrafluoroboric acid negatively charged ion, phosphofluoric acid negatively charged ion, trifluoromethanesulp-onyl-onyl imide negatively charged ion or trifluoromethane sulfonic acid negatively charged ion;
R is the methoxyl group alkyl with following logical formula III: CH
3o (CH
2)
n(III), wherein, n is 2,3 or 4.
In order to realize the 3rd object of the present invention, the technical solution adopted in the present invention is: a kind of il electrolyte, contain ionic liquid and organic solvent, and described ionic liquid is above-mentioned tetramethyleneimine ionic liquid.
Described organic solvent is acetonitrile, propylene carbonate or gamma-butyrolactone, and described tetramethyleneimine ionic liquid and organic solvent are according to mass ratio 1:5 ~ 2:1.
In order to realize the 4th object of the present invention, the technical solution adopted in the present invention is: a kind of electrical condenser, comprise by electrode slice, barrier film, electrode slice in order the stacked battery core forming, for installing the closed shell of described battery core, and filling is at the electrolytic solution of described closed shell, described electrode slice comprises collector and is coated in the slurry on this collector, described slurry comprises carbon nanotube, binding agent polyvinylidene difluoride (PVDF) and the conductive agent acetylene black that 85:5:4 mixes in mass ratio, and described electrolytic solution is above-mentioned tetramethyleneimine il electrolyte.
Compared with prior art,, there is following advantage in tetramethyleneimine il electrolyte of the present invention and preparation method thereof:
1. the il electrolyte that prepared by the present invention is compared with current commercial electrolytic solution, and owing to having added a large amount of ionic liquids, its stability and safety performance are greatly improved.
2. prepared il electrolyte is applied to ultracapacitor and has good chemical property.
Embodiment
Below in conjunction with embodiment, the present invention is given to elaboration further.
The preparation process of tetramethyleneimine il electrolyte of the present invention can roughly be divided into following three steps:
Crassitude → alkyl pyrrolidine halogenide → tetramethyleneimine ionic liquid → tetramethyleneimine il electrolyte
The first step is to prepare alkyl pyrrolidine halogenide by crassitude and haloalkane RX reaction;
Reaction formula is as follows:
Wherein, X is halogen, preferably chlorine, bromine or iodine atom; R is the methoxyl group alkyl with following logical formula II: CH
3o (CH
2)
n(II), wherein, n is 2,3 or 4;
The haloalkane RX is here methoxyl group haloalkane more precisely, and the oxygen in chemical formula is connected with carbon with ehter bond form.
Second step is that the ion-exchange of being undertaken by inorganic salt MY and alkyl pyrrolidine halogenide makes tetramethyleneimine ionic liquid;
Reaction formula is as follows:
In above-mentioned reaction, the positively charged ion M of inorganic salt MY
+for sodium ion (Na
+), potassium ion (K
+) or ammonium ion (NH
4 +); Y is Tetrafluoroboric acid negatively charged ion (BF
4 -), phosphofluoric acid negatively charged ion (PF
6 -), trifluoromethanesulp-onyl-onyl imide negatively charged ion ((CF
3sO
2)
2n
-) or trifluoromethane sulfonic acid negatively charged ion (CF
3sO
3 -).
The 3rd step is by above-mentioned tetramethyleneimine ionic liquid is mixed in organic solvent according to certain mass ratio, obtains being directly used in the tetramethyleneimine il electrolyte in electrical condenser.
Specifically set forth below the preparation process of tetramethyleneimine il electrolyte of the present invention:
(1) prepare alkyl pyrrolidine halogenide
1:1.05 ~ 1.2 add respectively crassitude and haloalkane in flask in molar ratio, at rare gas element N
2or Ar
2under atmosphere protection, be warming up to 60 ~ 80 ℃ to improve the activation energy of chemical reaction, add the speed of fast response.Stir 20 ~ 60h(churning time and can cause side reaction too for a long time) rear standing cooling, with ethyl acetate or methyl tertiary butyl ether washing several, then filter (reacted product is solid, only need filter and just reach separated object).Vacuum-drying 24 ~ 48h at 60 ~ 100 ℃, obtains alkyl pyrrolidine halogenide.Wherein, tetramethyleneimine and haloalkane preferred molar ratio be 1:1.1.
This step object is: by intensification, stir crassitude and haloalkane, to accelerate both speed of response, then use organic solvent ethyl acetate or methyl tertiary butyl ether washing reaction product for several times, thereby prepare required pure alkyl pyrrolidine halogenide.
(2) prepare tetramethyleneimine ionic liquid
The alkyl pyrrolidine halogenide, inorganic salt and the deionized water that obtain are joined in reaction flask by a mole volume ratio 1mol:1 ~ 1.1mol:200 ~ 300ml, at room temperature stir 5 ~ 20h, by 250ml dichloromethane extraction 3 times of reacted solution, combining extraction liquid, then use the back extraction of 60ml deionized water repeatedly, until with saturated AgNO
3till aqueous solution titration water produces without precipitation, collect methylene dichloride phase, this methylene dichloride is concentrated with Rotary Evaporators, (the concentrated effect of Rotary Evaporators is just equivalent to methylene dichloride to carry out underpressure distillation, to remove methylene dichloride), vacuum-drying 24 ~ 48h at 60 ~ 100 ℃, obtains tetramethyleneimine ionic liquid again.Wherein, alkyl pyrrolidine halogenide, inorganic salt and preferred molar ratio be 1:1.05.
The positively charged ion of inorganic salt is Na
+, K
+or NH
4 +; The negatively charged ion of inorganic salt is BF
4 -, PF
6 -, (CF
3sO
2)
2n
-or CF
3sO
3 -.
This step object is: choose after target inorganic salt, by the ion exchange reaction between alkyl pyrrolidine halogenide and target inorganic salt, to the product obtaining extract with the purification operations of stripping after, prepared required pure tetramethyleneimine ionic liquid.
(3) configuration tetramethyleneimine il electrolyte
At N
2or Ar
2under atmosphere protection, prepared tetramethyleneimine ionic liquid and organic solvent are mixed according to mass ratio 1:5 ~ 2:1, and stirred, thereby obtain object ion liquid electrolyte.Wherein, organic solvent is acetonitrile, propylene carbonate, gamma-butyrolactone etc.
This step object is: tetramethyleneimine viscosity of il is very large, adds can reduce its viscosity after organic solvent, improve specific conductivity, increase the wetting property of electrolytic solution, also can improve the performances such as electric capacity of ultracapacitor simultaneously.
The present invention also comprises the tetramethyleneimine il electrolyte of utilizing above-mentioned preparation method to make.
Preparation process with 1～4 pair of tetramethyleneimine il electrolyte of the present invention of embodiment describes below:
Embodiment 1
The tetramethyleneimine ionic liquid that the present embodiment 1 provides is specially: N-methoxy ethyl-N-crassitude a tetrafluoro borate liquid ions liquid, and its structural formula is:
The preparation method of above-mentioned ionic liquid, comprises the following steps:
(a) prepare alkyl pyrrolidine halogenide
In the flask of 250ml, add respectively 85g(1mol) crassitude and the methoxychlor ethane of 104.0g (1.1mol).At N
2under atmosphere protection, be warming up to 70 ℃, stirring reaction 40h.Standing cooling, with ethyl acetate washing three times.Vacuum-drying 24h at 80 ℃, obtains lurid solid and is N-methoxy ethyl-N-crassitude villaumite, and productive rate is 80%.
(b) prepare tetramethyleneimine ionic liquid
In 250ml flask, add 94.8g (0.5mol) N-methoxy ethyl-N-crassitude villaumite, 57.8g (0.53mol) NaBF
4with 130ml deionized water (being that three's molecular volume is than being 1mol:1.06mol:260ml), at room temperature stir 8h, by 250ml dichloromethane extraction 3 times of reacted solution, combining extraction liquid, then use the back extraction of 60ml deionized water repeatedly, until with saturated AgNO
3aqueous solution titration water is collected methylene dichloride phase till producing without precipitation, and this methylene dichloride is concentrated to remove with Rotary Evaporators, then vacuum-drying 48 hours at 80 ℃, obtains colourless N-methoxy ethyl-N-crassitude a tetrafluoro borate liquid.
The preparation method of il electrolyte:
At N
2under atmosphere protection, take out 10g N-methoxy ethyl-N-crassitude a tetrafluoro borate, then add wherein 20g acetonitrile, and be uniformly mixed, thereby obtain target tetramethyleneimine il electrolyte.
Embodiment 2
The tetramethyleneimine ionic liquid that the present embodiment 2 provides is specially: N-methoxy-propyl-N-crassitude hexafluorophosphate ionic liquid, and its structural formula is:
The preparation method of above-mentioned ionic liquid, comprises the following steps:
(a) prepare alkyl pyrrolidine halogenide
In the flask of 250ml, add respectively 85g(1mol) crassitude and 160.7g (1.05mol) methoxyl group N-PROPYLE BROMIDE.At Ar
2under atmosphere protection, be warming up to 60 ℃, stirring reaction 60h.Standing cooling, with ethyl acetate washing three times.Vacuum-drying 36h at 80 ℃, obtains lurid solid N-methoxy-propyl-N-crassitude bromine salt, and productive rate is 81%.
(b) prepare tetramethyleneimine ionic liquid
In 250ml flask, add 124.1g (0.5mol) N-methoxy-propyl-N-crassitude bromine salt, 92g (0.5mol) KPF
6with 100ml deionized water (being that three's molecular volume is than being 1mol:1mol:200ml), at room temperature stir 20h, by 250ml dichloromethane extraction 3 times of reacted solution, combining extraction liquid, then use the back extraction of 60ml deionized water repeatedly, until with saturated AgNO
3aqueous solution titration water is collected methylene dichloride phase till producing without precipitation, and this methylene dichloride is concentrated with Rotary Evaporators, then carries out 80 ℃ of vacuum-dryings 48 hours, obtains colourless liquid N-methoxy-propyl-N-crassitude hexafluorophosphate.
The preparation method of il electrolyte:
At Ar
2under atmosphere protection, take out 10g N-methoxy-propyl-N-crassitude hexafluorophosphate, then add wherein 50g propylene carbonate, and be uniformly mixed, thereby obtain target tetramethyleneimine il electrolyte.
Embodiment 3
The tetramethyleneimine ionic liquid that the present embodiment 3 provides is specially: N-methoxyl group butyl-N-crassitude fluoroform sulfimide salt ion liquid, and its structural formula is:
The preparation method of above-mentioned ionic liquid, comprises the following steps:
(a) prepare alkyl pyrrolidine halogenide
In the flask of 250ml, add respectively 85g(1mol) crassitude and 256.8g (1.2mol) methoxyl group butyl iodide.At N
2under atmosphere protection, be warming up to 80 ℃, stirring reaction 20h.Standing cooling, with ethyl acetate washing three times.Vacuum-drying at 120 ℃, obtains lurid solid and is N-methoxyl group butyl-N-crassitude salt compounded of iodine, and productive rate is 83%.
(b) prepare tetramethyleneimine ionic liquid
In 250ml flask, add 154.6g (0.5mol) N-methoxyl group butyl-N-crassitude salt compounded of iodine, 175.5g (0.55mol) (CF
3sO
2)
2nK and 150ml deionized water (being that three's molecular volume is than being 1mol:1.1mol:300ml), at room temperature stir 5h, by 250ml dichloromethane extraction 3 times of reacted solution, combining extraction liquid, then use the back extraction of 60ml deionized water repeatedly, until with saturated AgNO
3till aqueous solution titration water produces without precipitation, collect methylene dichloride phase, this methylene dichloride is concentrated with Rotary Evaporators, then carry out 80 ℃ of vacuum-dryings 30 hours, obtain colourless N-methoxyl group butyl-N-crassitude fluoroform sulfimide salt ion liquid.
The preparation method of il electrolyte:
At N
2under atmosphere protection, take out 10g N-methoxyl group butyl-N-crassitude fluoroform sulfimide salt, then add wherein 5g gamma-butyrolactone, and be uniformly mixed, thereby obtain object ion liquid electrolyte.
Embodiment 4
The tetramethyleneimine ionic liquid that the present embodiment 4 provides is specially: N-methoxy-propyl-N-crassitude trifluoromethanesulfonic acid salt ion, and its structural formula is:
The preparation method of above-mentioned ionic liquid, comprises the following steps:
(a) prepare alkyl pyrrolidine halogenide
In the flask of 250ml, add respectively 85g(1mol) crassitude and 119.4g (1.1mol) methoxychlor propane.At N
2under atmosphere protection, be warming up to 65 ℃, stirring reaction 45h.Standing cooling, with ethyl acetate washing three times.Vacuum-drying at 80 ℃, obtains lurid solid N-methoxy-propyl-N-crassitude villaumite, and productive rate is 82%.
(b) prepare tetramethyleneimine ionic liquid
In 250ml flask, add 101.8g (0.5mol) N-methoxy-propyl-N-crassitude villaumite, 86.8g (0.52mol) CF
3sO
3nH
4with 120ml deionized water (being that three's molecular volume is than being 1mol:1.04mol:240ml), at room temperature stir 15h, by 250ml dichloromethane extraction 3 times of reacted solution, combining extraction liquid, then use the back extraction of 60ml deionized water repeatedly, until with saturated AgNO
3aqueous solution titration water is collected methylene dichloride phase till producing without precipitation, and this methylene dichloride is concentrated with Rotary Evaporators, then carries out 80 ℃ of vacuum-dryings 48 hours, obtains colourless liquid N-methoxy-propyl-N-crassitude trifluoromethanesulfonic acid salt ion.
The preparation method of il electrolyte:
At N
2under atmosphere protection, take out 10g N-methoxy-propyl-N-crassitude fluoroform sulphonate, then add wherein 40g acetonitrile, and be uniformly mixed, thereby obtain tetramethyleneimine il electrolyte.
The preparation method of electrical condenser
(specific surface area is about 600m to take 8.5g carbon nanotube
2/ g), 0.4g acetylene black and 0.5g PVDF, join in 50g NMP, fully stir and make it to become the slurry mixing.Then by slurry blade coating on the collector aluminium foil cleaning through ethanol, under the vacuum of 0.01MPa, 100 ℃ are dried to constant weight, and are pressed into carbon nanotube electrode in 10MPa pressure lower roll, and are cut into electrode disk.In being full of the glove box of argon gas, pp barrier film and the arbitrary tetramethyleneimine il electrolyte of preparing of above-described embodiment 1 ~ 4 are placed between two carbon nanotube electrode disks, on stamping machine, button electrical condenser is made in sealing.
Utilize charge-discharge test instrument to carry out constant current charge-discharge test to the button electrical condenser assembling, in the electrochemical window of 0 ~ 2.7V, with the electric current of 0.5A/g, record it and discharge and recharge data and be listed in the table below 1.
Table 1
| Embodiment | 1 | 2 | 3 | 4 |
| Than electric capacity (F/g) | 85 | 78 | 80 | 74 |
As can be seen from the table, the prepared tetramethyleneimine il electrolyte of the embodiment of the present invention 1 ~ 4 is suitable for the electrolytic solution of ultracapacitor, and in the electrochemical window of 2.7V, has good capacitance characteristic.This explanation, in the present invention, prepared il electrolyte is applied to ultracapacitor and has good chemical property.In addition, compare with current commercial electrolytic solution, il electrolyte prepared by the present invention is owing to having added a large amount of ionic liquids, and its stability and safety performance are greatly improved.
Foregoing; it is only preferred embodiment of the present invention; not for limiting embodiment of the present invention; those of ordinary skills are according to main design of the present invention and spirit; can carry out very easily corresponding flexible or modification, therefore protection scope of the present invention should be as the criterion with the desired protection domain of claims.
Claims (10)
1. a preparation method for tetramethyleneimine ionic liquid, is characterized in that, comprises the steps:
(a) prepare alkyl pyrrolidine halogenide: crassitude and the haloalkane RX reaction with following logical formula I are made to the alkyl pyrrolidine halogenide with following logical formula II;
Wherein, X is halogen; R is the methoxyl group alkyl with following logical formula III:
CH
3o (CH
2)
n(III), wherein, n is 2,3 or 4;
(b) prepare tetramethyleneimine ionic liquid: the alkyl pyrrolidine halogenide that described step (a) is made and inorganic salt MY and deionized water carry out ion exchange reaction, obtain having the described tetramethyleneimine ionic liquid of following logical formula IV;
Wherein, Y
-for Tetrafluoroboric acid negatively charged ion, phosphofluoric acid negatively charged ion, trifluoromethanesulp-onyl-onyl imide negatively charged ion or trifluoromethane sulfonic acid negatively charged ion;
R is the methoxyl group alkyl with following logical formula III: CH
3o (CH
2)
n(III), wherein, n is 2,3 or 4;
M is sodium ion, potassium ion or ammonium ion.
2. preparation method according to claim 1; it is characterized in that; described step (a) is specially: under protection of inert gas; after 1:1.05 ~ 1.2 mixed methyl tetramethyleneimine and haloalkane RX, be warmed up in molar ratio 60 ~ 80 ℃ and stir 20 ~ 60h; standing cooling; with after ethyl acetate washing, through vacuum-drying, obtain alkyl pyrrolidine halogenide.
3. preparation method according to claim 2, is characterized in that, the preferred molar ratio of described crassitude and described haloalkane is 1:1.1.
4. preparation method according to claim 1, it is characterized in that, described step (b) is specially: getting described alkyl pyrrolidine halogenide, described inorganic salt and deionized water is to stir after 1mol:1 ~ 1.1mol:200 ~ 300ml mixes by mole volume ratio, to mixed solution described in the described dichloromethane extraction of 250ml for the mixed solution obtaining, the extraction liquid obtaining is stripped with 60ml deionized water, until with saturated AgNO
3till aqueous solution titration water produces without precipitation, the methylene dichloride of collecting is concentrated with Rotary Evaporators, after vacuum-drying, obtain tetramethyleneimine ionic liquid.
5. preparation method according to claim 4, is characterized in that, the preferred molar ratio of described alkyl pyrrolidine halogenide and described inorganic salt is 1:1.05.
6. preparation method according to claim 1, is characterized in that, described halogen X is chlorine, bromine or iodine atom.
7. the tetramethyleneimine ionic liquid with following logical formula IV that the arbitrary described preparation method of claim 1 to 6 makes,
Wherein, Y
-for Tetrafluoroboric acid negatively charged ion, phosphofluoric acid negatively charged ion, trifluoromethanesulp-onyl-onyl imide negatively charged ion or trifluoromethane sulfonic acid negatively charged ion;
R is the methoxyl group alkyl with following logical formula III: CH
3o (CH
2)
n(III), wherein, n is 2,3 or 4.
8. an il electrolyte, contains ionic liquid and organic solvent, it is characterized in that, described ionic liquid is tetramethyleneimine ionic liquid claimed in claim 7.
9. il electrolyte according to claim 8, is characterized in that, described organic solvent is acetonitrile, propylene carbonate or gamma-butyrolactone, the mass ratio 1:5 ~ 2:1 of described tetramethyleneimine ionic liquid and organic solvent.
10. an electrical condenser, comprise by electrode slice, barrier film, electrode slice in order the stacked battery core forming, for installing the closed shell of described battery core, and filling is at the electrolytic solution of described closed shell, described electrode slice comprises collector and is coated in the slurry on this collector, described slurry comprises carbon nanotube, binding agent polyvinylidene difluoride (PVDF) and the conductive agent acetylene black that 85:5:4 mixes in mass ratio, it is characterized in that, described electrolytic solution is the tetramethyleneimine il electrolyte described in claim 8 or 9.
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